Materials Today Communications 28 (2021) 102737

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Materials Today Communications

journal homepage: www.elsevier.com/locate/mtcomm

The mechanical properties and creep behavior of epoxy polymer under the
marine environment: A molecular dynamics investigation
Xueliang Li a, b, Xiaoyu Zhang a, b, *, Jianzhong Chen a, b, Li Huang a, b, Yong Lv a, b
a
School of Science, Wuhan University of Technology, Wuhan 430070, PR China
b
Hubei Key Laboratory of Theory and Application of Advanced Materials Mechanics, Wuhan University of Technology, Wuhan 430070, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: This study aims to investigate the creep evolution and related performance degradation of epoxy resin polymers
Marine environment in marine environment using molecular simulation. Based on the all-atomic models of epoxy resin, the effect of
Epoxy polymer different moisture absorption rate and different salt solution concentrations on the mechanical properties and
Creep
creep evolution is studied at several different tensile levels from the micro scale. The present simulation results
Molecular dynamics simulation
show that higher moisture absorption rate or salt solution concentration is more likely to lead to creep failure of
epoxy system. There is a threshold stress in the creep failure process of epoxy system, and the threshold stress in
salt solution environment is lower than that in water environment. The microscopic analysis reveals the
movement ability of epoxy resin fragments in the marine environment is stronger than that in the water envi­
ronment. In the process of creep failure accompanied by energy change, the bond energy of epoxy system re­
mains unchanged, while the non-bond energy increases gradually. These changes of microstructure and energy
together determine the macroscopic creep failure of epoxy resin system in marine environment. The results of
this study are expected to be a meaningful reference for the practical application of epoxy polymers in marine
environment and the further study of creep mechanism.

1. Introduction
Carbon fiber reinforced polymer (CFRP) composite is widely used in
aircraft manufacturing and marine structures because of its excellent
properties such as high stiffness ratio and high strength ratio [1–3], and
they will inevitably be corroded by the marine environment in the
process of use. Because of the good bonding properties of epoxy, it is
often used as substrates in the production of CFRP composites. However,
it is easier to creep under external load and easier to absorb water and
salt water than inert carbon fiber in marine environment, thus acceler­
ating the creep damage of materials and seriously affecting the reli­
ability and safety of the structure. Therefore, it is of great importance to
study the mechanical properties and creep evolution of epoxy resin in
marine environment comprehensively and to understand its creep fail­
ure mechanism.
Previous researchers have conducted extensive experimental studies
on the mechanical properties of CFRP composites in complex service
environments. Li et al. [4] performed the hygrothermal tests and ul­
trasonic three-point bending fatigue experiments to study the fatigue
behavior and employed several models for fatigue damage evolution
under cyclic loading, showing a better agreement of the continuum
damage mechanics (CDM) model with the measured damage. Zhang
et al. [5] investigated the effect of sample thicknesses on water ab­
sorptions and flexural strengths of CFRP laminates subjected to distilled
water or alkaline solution immersion. They proposed the
thickness-based accelerated method for hygrothermal aging test of CFRP
laminates, which is much more convenient to predict the long-term
performance of CFRP laminates and has higher accuracy than the
traditional temperature-based accelerated method. Wang et al. [6]
conducted that creep of the epoxy adhesive bonding layer causes an
increase in the slip between the fiber reinforced polymer (FRP) and the
structure, resulting the failure of the strengthening system during the
long-term service. Besides, experiments were conducted to study the
effect of water and salt environment of CFRP properties. Compared with
the dry environment, the mechanical properties of CFRP materials
decreased significantly after exposure to water and seawater for a period
of time [7–14]. The above researchers have done lots of research on the
mechanical properties of CFRP in complex environment, but few studies

* Corresponding author at: School of Science, Wuhan University of Technology, Wuhan 430070, PR China.
E-mail addresses: xueliang@whut.edu.cn (X. Li), zhangxiaoyu@whut.edu.cn (X. Zhang), jzhch@whut.edu.cn (J. Chen), wgdHL@whut.edu.cn (L. Huang),
lvyonghl@whut.edu.cn (Y. Lv).

https://doi.org/10.1016/j.mtcomm.2021.102737
Received 30 June 2021; Received in revised form 20 August 2021; Accepted 20 August 2021
Available online 25 August 2021
2352-4928/© 2021 Elsevier Ltd. All rights reserved.
X. Li et al. Materials Today Communications 28 (2021) 102737

on the creep properties and failure mechanism of CFRP or epoxy resin

Etotal = Ebond + Enon− bond
matrix in marine environment, which is urgent to be comprehensively
= Ebond− stretch + Eangle + Edihedral + Eout− + Evan− + Ecoulomb
investigated for further research.
of− plane der− waals

(1)
In recent years, with the increasing maturity of molecular dynamics
simulation method, it has been used to study polymer on the atomic
where Etotal is the total energy of the system, Ebond is the bond energy,
scale by more and more researchers, which provides a research means
Enon-bond is the non-bond energy, Ebond-stretch is the bond expansion en­
for studying the creep properties of epoxy resin matrix in water and salt
ergy, Eangle is the bond bending energy, Edihedral is the dihedral angular
environment. Pandiyan et al. [15] studied the water transport in the
torsion energy, Eout-of-plane is the out-of-plane vibration energy, Evan-der-
epoxy resin by preparing the epoxy polymer models with different water
waals is the van der Waals energy, and Ecoulomb is the Coulomb energy.
content using molecular dynamics simulation. Stoffels et al. [16] pre­
The curing agents Triethylenetetramine (TETA) and the Diglycidyl
sented molecular dynamics (MD) simulation methods for determining
Ether of Bisphenol F (EPON862) are used to build the structure of epoxy-
the solubility limit of water in a crosslinked epoxy network, resulting the
based polymer. The modeling process are presented subsequently. First,
conclusion that there has a moisture solubility of 3.50–3.75 wt% when
the molecular monomers of EPON862 and TETA were established
immersed in water at 300 K. Tam et al. [17] constructed the molecular
respectively. In the molecular modeling, the molecular polymerization
interface model of carbon fiber/epoxy bonded system and analyzed the
degree of all epoxy resin monomers was set to 0. In fact, as a simplified
interfacial integrity in salt environment. The simulation results show
model, n = 0 is a reasonable approximation. When the molecular dy­
that salt solution causes the largest bond loss, which is related to the
namics method is used to build the crosslinked epoxy network, the script
degradation of the structure and mechanical properties of the bond
crosslinking method is usually used to get a high crosslinking degree of
interface. Park et al. [18] conducted the cyclic simulations using mo­
the system. However, after many tests, it was found that this production
lecular models for epoxies cured by aliphatic and aromatic curing
method was too complex and required more time to be applied to larger
agents, triethylenetetramine (TETA) and diethyltoluenediamine
models. Therefore, a crosslinked epoxy element obtained in the simu­
(DETDA), respectively. These studies above show that the molecular
lation was used as a representative molecule for more effective simu­
dynamics method can be used to investigate the effect of water or salt
lation research [23]. Next, a method of representative molecule was
environment on polymer systems and the creep evolution mechanism of
used to make EPON862 and TETA curing agent cross-linked into a long
polymer properties. However, it is not very clear about the mechanical
chain called EPON862/TETA representative monomer. The chemical
properties and creep evolution of epoxy polymers in marine environ­
structures of these two monomers and the EPON862/TETA representa­
ment, which is of great significance for engineering practical
tive monomer are presented in Fig. 1. The representative monomer has
application.
three cross-linked bonds with the cross-linking ratio of 0.5. It should be
This paper mainly aims at investigating the effect of marine envi­
noted that the effectiveness of this representative molecular method has
ronment on epoxy resin polymer during creep process through the
been verified by previous researchers by measuring the Young’s
tensile creep simulation of the epoxy resin molecular model established.
modulus and glass transition temperature of the crosslinking agent,
A series of epoxy resin models with different moisture absorption rate
which are in good agreement with the calculated values of the cross­
and salt concentration can be established respectively. After verifying
linking method as well as those of previous molecular dynamics simu­
the rationality of these models, the physical and mechanical properties
lations and experimental observations [24]. Therefore, the
with moisture absorption rate and salt concentration are compared.
representative unit method is adopted in all molecular modeling in this
Then, the creep simulations of epoxy resin systems with different stress
paper. Then, a three-dimensional periodic unit cell consisting of 60
levels under saturated water absorption and medium concentration salt
EPON862/TETA representative monomers with an initial density of
environment are carried out, and the stress level threshold leading to
0.8 g/m3 was constructed by using the MS Amorphous Cell module with
creep failure of epoxy resin system in a certain time is determined. Based
COMPASS force field temporarily. As a result, the EPON862/TETA
on the above work, the creep mechanism of epoxy resin system in ma­
structure model with 9420 atoms has the size of
rine environment is investigated from the aspect of microstructure and
5.13 nm × 5.13 nm × 5.13 nm. The chemical structure of EPON862/­
microscopic energy at an atomistic level. Furthermore, the relationship
TETA and local enlarged drawings are shown in Fig. 2(a). So far, the
between mean square displacement (MSD) and strain of epoxy resin
initial molecular model of epoxy resin polymer had been constructed. In
fragments during creep can be well fitted by binomial formula, which
this paper, during the process of molecular simulation, Andersen and
provides a supplement for multi-scale study of epoxy system on creep.
Berendsen methods were used to control the temperature and pressure
This paper can provide a foundation for the study of viscoelastic
respectively, and Atom-based and Eward methods were used to calculate
behavior of epoxy resin in marine environment.
van der Waals and electrostatic interactions, respectively. The atom
partial charges are estimated through the bond increment technique
2. Simulation details
[25].
In order to study the influence of marine environment on the creep
2.1. Molecular model construction
process of epoxy resin, it is necessary to set up a reasonable simulation
environment. In this paper, the creep evolution of epoxy in water and
In this investigation, the Materials Studio version 2017 produced by
salt environment is simulated respectively, so molecular models in two
the American Accelrys Company and the parallel molecular dynamics
environments were established. To investigate the effect of different
code large atomic molecular massively parallel simulation (LAMMPS)
moisture absorption conditions on the creep process of epoxy polymer,
distributed by Sandia National Laboratories were used to carry out
different amounts of water molecules are added to the epoxy system.
epoxy resin molecular modeling and tensile creep simulation respec­
Previous studies have reported that the saturation hygroscopicity of
tively. The MSI2LMP tool of LAMMPS is used to convert models built by
epoxy resin systems exposed to water is less than 4% [26–29]. Therefore,
MS into the format required by LAMMPS. During the simulation in this
the amount of the water molecules added into the structure is 1.0 wt%
paper, the molecular interaction is simulated by using the consistent
and 4.0 wt% of the molar mass of the cross-linked network above, which
valence force field (CVFF) [19]. The applicability of CVFF potential in
are regarded as the different absorption condition. At the same time,
the study of epoxy system has been verified in previous simulation
according to the actual situation in the marine environment, 5.0 wt%,
studies [20–22]. The potential function of the CVFF force field is
7.0 wt% and 9.0 wt% NaCl solution were selected to simulate the salt
composed as shown in formula (1),
environment. The molecular models of the epoxy system in the corre­
sponding environment are shown in Fig. 2(b)–(f). The interatomic

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X. Li et al. Materials Today Communications 28 (2021) 102737

Fig. 1. Chemical structures of molecular monomers (a) EPON862 (b) TETA and (c) EPON862/TETA representative monomer. Oxygen: red; Carbon: gray; Nitrogen:
blue; Hydrogen: white. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 2. Molecular models of epoxy resin before equilibrium in (a) dry environment, (b) and (c) water environment, (d), (e) and (f) salt environment. Oxygen: red;
Carbon: gray; Nitrogen: blue; Hydrogen: white; Sodium: purple; Chlorine: green. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

parameters of these models in this simulation are reported in Supporting within LAMMPS using the CVFF potential and then equilibrated with a 1
Information. The water molecule in this study employs the TIP3P model fs time step using NPT ensemble and zero pressure until the density, and
[30]. Table 1 are the parameters of water model and salt ions used in this total energy of the system fluctuated around a constant value. The spe­
paper. cific equilibrium process is as follows: the initial model is relaxed for
After the initial construction process, the models were minimized 500 ps at 300 K, then heated to 500 K at the rate of 1 K/ps and relaxed
for 500 ps at this temperature and cooled to 300 K at the rate of 1 K/ps
and relaxed 500 ps again. After completing the above steps, the equi­
Table 1 librium molecular models were obtained.
Parameters of TIP3P water model and salt ions used in this paper.
Type ε (kcal mol− 1) σ (nm) Electric charge 2.2. Physical and mechanical properties
Oxygen 0.102 0.319 -0.82
Hydrogen 0.000 0.000 0.41 To verify the correctness of the epoxy resin model, the equilibrium
Sodium ion 0.087 0.248 1.00 density, glass transition temperature (Tg), yield strength and Young’s
Chloride ion 0.036 0.462 -1.00
modulus of epoxy resin systems were calculated. In addition, the

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X. Li et al. Materials Today Communications 28 (2021) 102737

distribution of water molecules in epoxy resin system with different

water absorption was characterized.
In the process of equilibrium, the density of the epoxy resin system
would gradually increase from the initial 0.8 g/cm3 until it was finally
maintained at a constant level. The final density was determined ac­
cording to the average of the final 100 ps density in the whole equilib­
rium process. In fact, during the relaxation process of the NPT ensemble
mentioned above, the density of the system would soon reach a certain
constant value. In this paper, the equilibrium method of multiple NPT
rising and cooling was used to ensure that the system can fully relax to
get the optimal structure, so as to simulate the real epoxy resin system.
Then, the glass transition temperature was calculated by recording
the density at varied temperature conditions using LAMMPS [31]. In
particular, the equilibration process was conducted at temperature ris­
ing from 300 K to 500 K at a rate of 1 K/ps for 200 ps, and lasted for
500 ps at 500 K. After that, the equilibration process was performed
with the temperature decreasing to 200 K at a rate of 1 K/ps for 300 ps.
Then, the equilibration process was performed with the temperature
rising from 200 K to 600 K. The equilibration was run for 500 ps at each
temperature increase of 25 K, and the density was recorded every 1 ps,
Fig. 4. The uniaxial tensile stress-strain relationship of EPON862/TETA epoxy
and the last 50 ps data of density are were averaged to calculate density resin system under dry environment.
of the epoxy model in a steady level during the process. The relationship
between density and temperature is shown in Fig. 3, where the glass
model, etc. The Ludwik hardening model has been used to successfully
transition temperature was obtained by finding the intersection point
simulate the corresponding mechanical properties of the polymer by
between two fitting lines.
other authors [33]. Ludwik’s hardening model derived from Hollomon’s
After the glass transition temperature of the model was simulated,
model is a typical unsaturated extrapolation model of fixed initial
the yield strength and Young’s modulus of the epoxy resin model were
values, which ensures that the plastic strain segment passes through the
determined. To better understand the creep behavior of epoxy, the
yield point of the material. Based on the Ludwik’s hardening model and
uniaxial tensile simulation s was conducted by stress-controlled defor­
previous research work, the yield stress of the epoxy resin structure was
mation. At the same time, Young’s modulus was calculated based on the
determined by fitting the linear elasticity and Ludwik’s hardening
relatively linear part of the stress–strain curve from the tensile defor­
model, and the expression is as follow,
mation [31].
( )n
During the uniaxial tensile deformation, a small strain rate is used to σ = σ y + h εp (2)
the mechanical test, so as to avoid the influence of large strain rate on
the stress response [32]. Therefore, uniaxial tensile deformation in the X where σ y , h, εp , and n are the yield stress, strength coefficient, plastic
direction up to 0.15 strain was carried out at a strain rate of 3 × 108 /s strain, and hardening exponent respectively. The yield strength of the
(see Fig. 4) at 300 K in NPT ensemble for 500 ps to determine the stress epoxy resin model was chosen as the minimum deviation point between
levels applied on the epoxy resin, while the Y and Z directions were zero the original MD data obtained by simulation and the Ludwik’s hard­
pressure. The yield strength of the polymer can be obtained by fitting the ening model.
flow stress curve obtained by uniaxial tensile test. For the strain
behavior of epoxy resin polymers under small deformation (plastic 2.3. Setup of creep simulation
strain less than 0.2), many scholars have proposed various extrapolation
models, such as Hollomon model, Swift model, Ludwik hardening On the basis of the epoxy resin models above, the creep behavior of
epoxy resin system in marine environment was studied by uniaxial
tension method. In the specific simulation process, the epoxy resin
system can be regarded as an isotropic material, and a constant stress
level lower than the yield strength is applied along the X direction of the
epoxy resin system, while ensuring that the stress level in the Y and Z
directions is always zero to simulate the creep process of uniaxial ten­
sion. It should be noted that all of the creep simulations described above
are controlled by applying atmospheric pressure in the corresponding
direction programmed in LAMMPS.

3. Results and discussion

3.1. Basic characteristics and mechanical properties

Through the previous equilibrium and simulation calculation of the

Fig. 3. Density versus temperature relationship for EPON862/TETA model in
dry environment.
epoxy resin system, the basic physical and related mechanical properties
of the model were obtained, which could be used to verify the correct­
ness of the model. At the same time, it could be obtained that the me­
chanical properties of epoxy resin polymer change with the change of
moisture absorption rate and salt solution concentration.
Density verification of the model system. The final densities of the
epoxy systems in the water and salt environment are shown in Table 2.
According to the simulation results, the density of the fully relaxed

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X. Li et al. Materials Today Communications 28 (2021) 102737

Table 2
Physical and mechanical properties in water environment.
Type Wm Density Glass transition Young’s
(wt%) (g/cm3) temperature (K) modulus (Gpa)

Moisture 0.0 1.147 410 3.390 ± 0.134

absorption rate 1.0 1.150 398 2.674 ± 0.103
4.0 1.146 349 2.433 ± 0.089
Salt solution 5.0 1.113 352 2.231 ± 0.121
concentration 7.0 1.141 335 2.101 ± 0.048
9.0 1.141 324 1.850 ± 0.056

epoxy resin model is 1.147 g/cm3 under dry conditions and the density
of all epoxy resin systems is between 1.1 g/cm3 and 1.2 g/cm3, which is
consistent with the conclusions obtained by previous researchers and
experiments [34].
Glass transition temperature verification. The glass transition tem­
perature of each system was calculated and processed according to the
previous method in 2.2 of this paper. As shown in Fig. 3, the glass
transition temperature of the polymer system in dry environment is
about 410 K. The glass transition temperature is close to 417 K obtained
by other researchers through molecular dynamics simulation [31],
which shows the rationality of the epoxy resin model structure estab­
lished here. At the same time, the glass transition temperatures of other
models were obtained, which were shown in Table 2. The glass transi­
tion temperature of epoxy resin system decreases with the increase of
moisture absorption and salt solution concentration.
Characterization of yield strength and Young’s modulus. It can be
seen from Fig. 4 that the yield strength of the epoxy resin model under
dry environment is 206.64Mpa and the corresponding strain is 0.052. It
should be noted that the yield strength of the epoxy resin simulated in
this paper is slightly lower than the 264.26Mpa reported by others [18],
which may be since the cross-linking degree of the model established by
the representative monomer method in this paper is slightly lower than
that of the previously reported model (81.3%). Besides, the stress-strain
curves of epoxy polymer systems in water and salt environment are
shown in Figs. 5 and 6. According to the simulation results, it is found
that the Ludwik’s hardening model cannot get the specific values of the
yield strength of the systems in water environment and salt solution
environment, so only qualitative analysis is made here. The simulation
results show that the yield strength of epoxy systems in two environ­
ments is lower than that in dry conditions, and the yield strength de­
creases with the increase of moisture absorption rate or salt solution
concentration. It can be seen from Table 2 that the Young’s modulus of
the epoxy resin model under dry condition is 3.390 ± 0.134 GPa, which
Fig. 6. Tensile stress-strain curve of epoxy resin polymer in salt environment.
is consistent with the 3.362 GPa simulated by previous researchers and
the experimental value 3.24 GPa [24]. In addition, the Young’s modulus
of epoxy resin decreases gradually with the increase of moisture ab­
sorption rate and salt solution concentration, and the Young’s modulus
of the system in salt solution environment is obviously lower than that in
water environment.
The structural verification of the equilibrated model. As shown in the
Fig. 7 are schematic diagrams of molecular structure of the initial
configuration (Fig. 7a and b) and fully equilibrated (Fig. 7c and d) with
1.0 wt% and 4.0 wt% moisture absorption rate shown in the visualiza­
tion software OVITO. Here, the water molecules in the in the initial
epoxy resin model are uniformly dispersed in the structure. After full
equilibration, the molecular configuration of different moisture ab­
sorption rate changes. The simulation results show the different struc­
tures of water molecules in the different moisture absorption rate of
epoxy network systems. Specifically, in the system with low moisture
absorption, the water molecules in the system are still uniformly
dispersed in the structure; while in the system with high moisture ab­
sorption, the water molecules in the system form clusters with large size.
The different structures and conformations of water molecules at various
water concentrations are in good agreement with the experimental
phenomena observed by optical microscope in previous experimental
studies.
Through the above verifications of the physical and mechanical
properties and structure of the epoxy system, it is proved that the models
established in this paper are reasonable, which lays a foundation for the
follow-up creep simulation research.

3.2. Creep behavior of epoxy model

During the creep process of epoxy system, the effects of different

Fig. 5. Tensile stress-strain curve of epoxy resin polymer in water environment.
moisture absorption rate and salt solution concentration on the prop­
erties of epoxy resin were studied. In order to study its effect clearly, the
constant load with high stress level was used to simulate the tensile
creep of epoxy resin polymer until failure. At a high stress level, the
epoxy resin system will have a complete creep stage in a very short time.
By comparing the sequence of failure, the effects of moisture absorption
and salt solution concentration on the properties of epoxy resin polymer
can be determined. The epoxy resin systems in two environments were
applied a constant load at the same stress level according to the method
of Section 2.3 in this paper. The creep failure of polymers in both en­
vironments is shown in Figs. 8 and 9.
As is shown in Fig. 8, the performance of the epoxy resin system
begins to deteriorate with the increase of moisture absorption until it

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X. Li et al. Materials Today Communications 28 (2021) 102737

Fig. 7. The schematic diagrams of molecular structure of the initial configuration (a, b) and fully equilibrated (c, d) with 1.0 wt% and 4.0 wt% moisture absorption
rate shown in the visualization software OVITO. Grey sticks represent epoxy molecules fragments while the red spheres the water molecules. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 8. The variation curve of strain versus time in the creep process of epoxy Fig. 9. The variation curve of strain versus time in the creep process of epoxy
system with moisture absorption of 1.0 wt% and 4.0 wt% at the same constant system with salt solution concentration of 5.0 wt%, 7.0 wt% and 9.0 wt% at the
stress level. same constant stress level.

reaches the state of saturated water absorption. The simulation results
show that when the epoxy resin system bears the same external load as
the dry epoxy resin system, the mechanical properties of epoxy resin will
decrease when exposed to water environment. With the increase of time,
the moisture absorption increases, which is more prone to damage. It
can be seen from Fig. 9 that the creep process of epoxy resin system is
similar to that with the increase of moisture absorption with the increase
of salt concentration. It shows that the high concentration of salt solu­
tion will destroy the mechanical properties of the polymer, and then
accelerate the creep failure process of the epoxy resin polymer.
To further study the creep process of epoxy resin polymers, a series of
constant loads with different stress levels were applied to simulate the

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X. Li et al. Materials Today Communications 28 (2021) 102737

creep process of polymer systems in different environments. The

determination of the models here is based on the previous simulation
results, selecting the system of 4.0 wt% saturated water absorption in
water environment and the system with concentration of 5.0 wt% in salt
environment respectively. It needs to be explained that the saturated
water absorption is selected to simulate the response of the epoxy system
under dangerous conditions to different stress levels, while the epoxy
system with 5.0 wt% concentration in salt environment is a common
choice for many researchers to simulate the marine environment
[35–38]. Figs. 10 and 11 show the creep response of epoxy resin system
to different stress levels in water environment and salt environment,
respectively.
As can be seen from Figs. 10 to 11, at low stress levels, only the first
and second creep stages can be observed and remain unchanged for a
long time; while the epoxy resin will have a complete creep stage at high
stress level, which will be destroyed rapidly. Through several approxi­
mate creep simulations, it is found that there is a stress threshold for
tensile creep of epoxy resin system, and the stress threshold is different
in water environment and salt environment. The stress threshold of
epoxy system in saturated water absorption environment is between
68% and 73% of yield strength, while that of epoxy system in salt Fig. 11. The variation curve of strain versus time in the creep process of epoxy
environment is between 65% and 68% of yield strength. The simulation resin system with 5.0 wt% concentration in salt environment under a series of
constant stress levels.
results show that the salt environment is more disadvantageous to the
long-term performance of the epoxy resin system than the water envi­
ronment, which provides some reference for practical engineering
applications.

3.3. Microstructure parameter analysis

The microstructure of materials is not only an important internal

reason that affects their properties, but also a prerequisite for the pre­
diction and analysis of material properties. To further investigate the
influence of epoxy resin system on creep process in water environment
and salt environment from the point of view of microstructure, the
epoxy systems in different environments were studied from the point of
microstructure parameters.
The free volume here is calculated by the quantum chemical wave
function analysis program Multiwfn. Fig. 12 is a schematic diagram of
the calculated free volume of epoxy system. Because the total volume
and free volume of epoxy resin model are constantly changing during
creep, the free volume of each system cannot be compared directly.
Therefore, the percentage of free volume is used to express the relative

Fig. 12. A schematic diagram of the free volume of epoxy system calculated by
the quantum chemical wave function analysis program Multiwfn.

Fig. 10. The variation curve of strain versus time in the creep process of epoxy
resin system with 4.0 wt% saturated water absorption in water environment
under a series of constant stress levels.
size of free volume here. Fig. 13(a) and (b) show the percentage of free
volume of epoxy resin systems in two environments, and a comparative
analysis is made in the case of drying. With the increase of water ab­
sorption, it can be seen that the free volume percentage of the polymer
system gradually decreases, indicating that the water molecules entering
the epoxy resin system occupy part of the voids of the epoxy system.
With the increase of the concentration of salt solution, the percentage of
free volume in epoxy system increased at first and then decreased
gradually. The increase in the percentage of free volume is due to the
participation of water molecules in the solution in the swelling reaction,
and the subsequent decrease may be due to the inhibition of the swelling
reaction by high concentration of salt solution, while the larger ions in
the solution occupy the free volume. It is worth noting that the larger
free volume ratio of the epoxy system in 5.0 wt% salt solution corre­
sponds to the smaller density of the system in Table 2.
The mean square displacement (MSD) can be used to describe the
motion ability of each atomic and molecular chain segment in the sys­
tem. The MSD of epoxy molecular fragments and water molecules in the
tensile creep process of two environmental epoxy systems were

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X. Li et al.
Fig. 13. The free volume percentage of epoxy resin systems with different moisture absorption rate and salt solution concentration in (a) water environment and (b)
salt solution environment.
calculated respectively. Figs. 14 and 15 show the time-dependent MSD
curves of epoxy fragments and water molecules in the three directions of
x, y, z in the previous creep process, respectively. It should be noted that
when the MSD reaches the maximum value with time, the strain of the
corresponding system is 1, which is consistent with the creep curve with
time in Section 3.2 earlier in this paper. It can be obtained that the MSD
of epoxy fragments and water molecules along the tensile direction are
larger than those in the other two directions. The results show that the
epoxy resin fragments are rearranged along the stretching direction.
This is due to the fact that under the action of external forces, the center
of gravity of polymer chains such as epoxy resin will move relatively
along the direction of external forces, which is conducive to the move­
ment of molecular chains to the direction of force. Fig. 14 show that the
maximum MSD of epoxy molecular fragments in salt environment is
287.806 Å2, which is larger than 186.745 Å2 in water environment. As
can be seen from Fig. 15, the maximum MSD of water molecules in salt
environment is 1397.84 Å2, which is larger than that of 665.023 Å2 in
Fig. 14. The time-dependent MSD curves of epoxy fragments in the three directions of x, y, z in the creep process.
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Materials Today Communications 28 (2021) 102737
water environment. It can be found that the MSD of water molecules in
epoxy system is much larger than that of epoxy molecular fragments,
which is due to the smaller volume of water molecules and stronger
movement space and ability than cross-linked epoxy molecular
fragments.
Fig. 16 shows the variation curves of the total MSD of epoxy systems
with time in water environment and salt environment, respectively. It
should be noted that in order to make an objective comparison, the
normalized numerical processing of MSD is done here, and the original
data and the processed data are displayed together. As shown in Fig. 16,
the epoxy system with higher moisture absorption rate or higher salt
solution concentration can have larger MSD in a very short time, which
reveals that higher moisture absorption rate and salt solution concen­
tration are more disadvantageous to the epoxy system. This can be
explained by the conclusion of previous researchers: when the moisture
absorption rate of the epoxy resin structure is low, most of the water
molecules form hydrogen bonds with the epoxy network, resulting in
X. Li et al.
Fig. 15. The time-dependent MSD curves of water molecules in the three directions of x, y, z in the creep process.
Fig. 16. The variation curves of the total MSD of epoxy systems versus time in (a) water environment and (b) salt environment, respectively.
low hydrogen bond kinetics and water fluidity of the epoxy resin. With
the increase of moisture absorption rate, water molecules will form more
water-water hydrogen bonds, resulting in the formation of larger clus­
ters in the system as shown in Fig. 7 in this paper, thus accelerating the
hydrogen bonding kinetics of epoxy resin and improving the fluidity of
water. Interestingly, by comparing Figs. 8 and 9 with Fig. 16, it is found
that the relationship of MSD of epoxy molecular fragments with strain
can be fitted almost perfectly by the quadratic relation, which satisfies
the formula (3),
MSD(ε) = Aε2 + Bε + C
where A, B, C are the quadratic term coefficient, the first order term
coefficient and the constant term of the quadratic equation of one var­
iable, respectively. Figs. 17 and 18 show the curves of the variation of
epoxy molecular fragment MSD with the system strain in water and salt
environments, respectively, and the corresponding results fitted by
quadratic relations. Table 3 is the corresponding coefficients obtained
by fitting the simulated data. The results show that the relationship
between the MSD of epoxy resin fragments and the strain of the system is
Materials Today Communications 28 (2021) 102737
consistent in water and salt solution environment, and it hardly changes
with the increase of moisture absorption rate or salt solution concen­
tration. From this point of view, this conclusion reveals the mathemat­
ical relationship between the strain in the macro scale and the MSD in
the micro scale, which provides a reference for the multi-scale study of
epoxy resin system.
From Figs. 14 to 18, it can explain the conclusion in Section 3.2 that
the stress threshold in salt environment is lower than that in water
environment. From the view of microscopic molecular motion, it is
revealed that the creep performance of epoxy resin system in salt envi­
(3)
ronment is worse than that in water environment. The above studies
provide a basis for the further study of the creep failure mechanism of
epoxy polymers.
During the creep process, the structure and properties of epoxy
polymer system can be characterized not only by the change of micro­
structure, but also by the change of microscopic energy. In this paper,
the bond energy and non-bond energy of epoxy polymer systems in two
environments were calculated and characterized, respectively. It can be
seen from Fig. 19 that with the increase of moisture absorption of epoxy
9
X. Li et al. Materials Today Communications 28 (2021) 102737

Fig. 17. The curves of the variation of epoxy molecular fragment MSD versus the system strain in water environment with (a) original data and (b) the corresponding
results fitted by quadratic relations.

Fig. 18. The curves of the variation of epoxy molecular fragment MSD versus the system strain in salt environment with (a) original data and (b) the corresponding
results fitted by quadratic relations.

moisture absorption rate, the increase of OH bonds in water molecules

Table 3
and the possible formation of more hydrogen bonds between molecules.
The coefficients fitted by polynomial formula of MSD versus strain curve of
The creep process of epoxy system is accompanied by the change of non-
epoxy molecular fragments in water and salt environment.
bond energy, as shown in Fig. 20. The simulation results show that the
Type Wm A B C R2 non-bond energy increases with the increase of strain in the creep pro­
(wt%) (%)
cess, which indicates that the interaction of van der Waals force and
Moisture 1.0 190.546 41.256 -1.005 ± 0.046 99.98 Coulomb force decreases and the performance of the system is gradually
absorption rate 4.0 208.312 28.369 -0.168 ± 0.072 99.97
destroyed.
Salt solution 5.0 251.511 48.807 -0.966 ± 0.114 99.93
concentration 7.0 210.225 32.060 -0.552 ± 0.090 99.97
9.0 197.516 44.624 -1.296 ± 0.149 99.92 4. Conclusions

In this study, the effect of marine environment on mechanical

polymers, the bond energy of all polymer systems remains unchanged degradation and creep evolution of epoxy resin was studied successfully
during creep under CVFF force field. Furthermore, in the water envi­ by molecular dynamics method. Molecular models of epoxy resins in
ronment, the bond energy of the system with 4.0 wt% moisture ab­ different environments were established to study the effects of water
sorption rate is larger than that of 1.0 wt%. This is due to the increase of

10
X. Li et al.
Fig. 19. The variation curve of bond energy versus strain in water environment
and salt environment during the creep process of epoxy system.
Fig. 20. The variation curve of non-bond energy versus strain in water envi­
ronment and salt environment during the creep process of epoxy system.
absorption and salt concentration on the physical and mechanical
properties. The glass transition temperature, Young’s modulus and yield
strength of epoxy resin system decrease with the increase of moisture
absorption rate and salt solution concentration. The stress threshold of
epoxy resin system in creep process was determined, resulting that the
stress threshold in salt environment was lower than that in the moisture
absorption system. These creep phenomenon of the above epoxy resin
system in marine environment can be explained from the micro scale. By
monitoring the MSD in the creep process, salt solution can significantly
improve the mobility of epoxy resin fragments, compared with that in
water. In the process of creep failure, the bond energy of epoxy system
remains unchanged, while the non-bond energy gradually increases and
approaches 0, which reveals that one reason for creep failure is the
continuous weakening of the interatomic interaction. In general, the
study in this paper can provide a reference for the experimental visco­
elastic study of epoxy resin system and serve as a basis for further study
of creep failure mechanism in marine environment.
Supplementary material
See Supporting Information for the interatomic parameters of these
11
Materials Today Communications 28 (2021) 102737
models in this paper.
CRediT authorship contribution statement
Li Xueliang: Conceptualization, Investigation, Writing – original
draft, Writing – review & editing Zhang Xiaoyu: Conceptualization,
Validation, Supervision, Funding acquisition Chen Jianzhong: Valida­
tion Huang Li: Validation, Writing – review & editing Lv Yong: Writing
– review & editing. All authors have read and agreed to the submitted
version of the manuscript.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was funded by the National High-tech Research and
Development Program of China (863 Program) (No. 2013AA031306)
and Fundamental Research Funds for the Central Universities (No.
WUT:2014-Ia-014).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.mtcomm.2021.102737.
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